This invention relates to generally to the leaching of a base metal.
The invention relates to a hydrometallurgical method for heap leaching of copper from principally sulphide minerals such as chalcocite, covellite, bornite and chalcopyrite, or a mixed sulphide with copper oxide mineral. These applications are however exemplary only and are non-limiting for the principles of the invention may be used for the recovery of base metals such as nickel from nickel sulphide minerals e.g. pentlandite and millerite, and for the recovery of zinc from zinc sulphide minerals. The invention is described hereinafter with reference to the use of a high chloride mediated, high solution potential, pre-treatment step for heap leaching of run-of-mine (ROM) or crushed ore.
An object of the invention is to increase the oxidation rate of sulphide minerals or mixed sulphide and oxide minerals during a pre-treatment step prior to active heap irrigation, and thereby provide improved metal recovery in a shorter leach cycle and, additionally, to address the operational cost of a heap leach by reducing aeration requirements.
The invention is primarily based on the surprising discovery that copper extraction from copper sulphide minerals may be enhanced at solution potentials exceeding 700 mV SHE, in the absence of any microorganism, by contacting the minerals in a pre-treatment phase using an acid solution at a high chloride content containing dissolved copper.
As used herein “a heap” includes a heap, a dump, a vat or a column which contains an ore which is to be processed.
The invention provides a method of recovering a base metal from an ore wherein the ore is subjected to a pre-treatment phase followed by an active leach cycle and wherein, in the pre-treatment phase:
A low dissolved oxygen level in the solution may be achieved by natural ventilation of the heap, or if required by applying a low aeration rate to the heap or to the irrigation solution
The solution may contact the ore after the heap has been established. Alternatively or additionally the solution may contact the ore using an agglomeration technique, or by contacting the ore directly, while the heap is being established or after the heap has been established. The aforementioned step 1 is to be construed in this manner.
The method may include the step of providing an irrigation grid whereby the solution is applied to the heap. The irrigation grid may be located on a surface of the heap, or within the heap, or a combination of both locations may be employed. The irrigation grid may be used directly on an established heap, or in combination with an agglomeration technique.
The irrigation grid may be of any suitable kind and the invention is not limited in this respect. By way of example the irrigation grid may include a reticulated network of pipes, sprays and the like located on a surface of the heap, or within the heap, or both.
The method may include the steps of monitoring the moisture content in the heap and of controlling the addition of solution to the heap in response to the measured moisture content.
The rate at which solution is supplied to the heap during the pre-treatment process may be varied in response to the measurement. Alternatively, the supply of solution to the heap may be interrupted at intervals i.e. the solution is supplied in a batch mode to the heap. A combination of both techniques may however be employed.
The chloride ions may be introduced, within the pre-treatment process, by means of one or more of the following:
The pH level of the solution in contact with the ore may be maintained at pH 3.0, preferably less than pH 2.5, by the addition of sulphuric acid directly to the ore during an agglomeration process or by the addition of sulphuric acid to the solution which establishes the moisture level. As noted, the solution may be applied to the ore during an agglomeration process or by means of the irrigation grid or by using both techniques.
The pre-treatment phase may be carried out under ambient conditions i.e. at temperature and atmospheric pressure conditions prevailing at the heap.
It is possible to generate heat on surfaces of the ore particles during an agglomeration process, by contacting the ore with a solution which has the aforementioned high Cl ion concentration and to which concentrated sulphuric acid has been added. The amount of heat generated during the agglomeration process is caused by a reaction on the ore surface of the added sulphuric acid with the chloride and copper in solution. This is important for the heat generated raises the ore temperature significantly and the increased temperature contributes to faster mineral oxidation rates and, consequently, to an increase in metal recovery and to a reduction in leach cycle time.
When the method of the invention is employed for the recovery of copper the solution may have a copper to iron ratio >1.
The desired copper to iron ratio may be obtained by means of one or more of the following processes:
Preferably the pH of the solution which is brought into contact with the ore during the pre-treatment phase is less than pH 2.5
The pre-treatment phase is preferably carried out for a period of less than 100 days. The duration of the pre-treatment period is determined by the time to complete mineral oxidation and is dependent, at least, on the method used to contact the ore with the solution i.e. by using an agglomeration technique, by direct solution contact with the ore, or by irrigation of the heap.
During the active leach cycle, which follows the pre-treatment phase, the ore in the heap may be irrigated with a leach solution. The subsequently-leached base metal, e.g. copper, may thereafter be recovered using any suitable process e.g. a solvent extraction process.
The leach solution used in the active leach cycle may contain sulphuric acid and have a pH of less than pH 2.5.
Optionally, hydrochloric acid may be added to the leach solution.
The leach solution may contain copper, iron and other anion and cation species that may originate from process water drawn from the heap, or which may have dissolved from the ore which is being treated.
The solvent extraction process may include at least one copper-loaded organic washing stage to promote an electrolyte chloride ion concentration which is below 50 ppm.
The invention is further described by way of example with reference to the accompanying drawings in which:
The invention is described herein with reference to the use of a high chloride mediated, high solution potential, pre-treatment phase, prior to an active leach cycle, for crushed or run-of-mine (ROM) ore, heap leaching. The invention is based on the surprising discovery that, in respect of copper recovery, the conditions referred to herein enhance copper extraction from copper sulphide minerals and from copper sulphide/copper oxide minerals in a shorter leach cycle at solution potentials exceeding 700 mV SHE, in the absence of any sort of microorganism.
An object of the invention is to significantly increase the oxidation rate of sulphide minerals or mixed sulphide and oxide minerals during a pre-treatment step prior to active heap irrigation, and thereby improve metal recovery in a shorter leach cycle and, additionally, to lower, at least to some extent, the operational cost of a heap leach by reducing or eliminating the requirement of forced aeration during a pre-treatment step. This type of aeration is normally implemented through the use of blowers, compressors and similar devices. The reduction of aeration is possible since in the method of the invention the pre-treatment reaction proceeds at lower dissolved oxygen levels, and at a lower oxygen demand, compared to conventional heap leach practice. Consequently, forced aeration of the heap at the high aeration rates which are normally required to maintain solution oxidation potentials at 700 mV vs. SHE or greater, is not necessary.
The pre-treatment phase can be carried out, at least partly, using agglomeration techniques, while a heap is being constructed. Alternatively or additionally the pre-treatment phase can be implemented after the heap has been constructed. During the pre-treatment phase which may be from 1 to 200 days in duration but which is preferably less than 100 days in duration, and prior to active heap irrigation, the invention aims to achieve rapid oxidation of sulphide minerals or mixed sulphide and oxide minerals. The duration of the period of pre-treatment is determined by the time to complete mineral oxidation and is dependent, at least, on the method used to contact the ore with the solution e.g. by using an agglomeration technique, by direct solution contact with the ore, or by irrigation of the heap.
An irrigation network 14 is positioned to irrigate the heap with a solution 16 prepared with water drawn from a source 18. The irrigation network includes a reticulated system built from irrigation pipes 20 dispersed above and within the heap, and sprays or outlet nozzles 22 of any suitable kind. Moisture sensors 24 and related instruments are positioned on or in the heap, as appropriate, in order to obtain a measure of the moisture content of the ore in the heap.
The pre-treatment phase is implemented under the control of a control system 26. This system, in response to various parameters and variables, controls the addition of chloride ions 28, sulphuric acid 30 and copper-containing material 32, to the water 18 to produce the solution 16 with desired characteristics. The system is also responsive to characteristics of a solution 34 draining from the heap.
The ore 12 may, as noted, be placed in the heap using an agglomeration process i.e. the ore particles are treated with the solution 16 while the heap is being constructed. Alternatively the heap is constructed from the ore particles and thereafter the solution 16 is applied to the heap. Both approaches can however be used, in succession.
In the pre-treatment phase the solution 16 is used to irrigate the ore for a period of up to 200 days. The solution, which contacts the ore, complies with the following characteristics:
The solution is applied to the heap to achieve an ore moisture content of between 2 wt. % and 25 wt. %. Preferably the ore moisture content lies in the range of from 5 wt. % to 8 wt. %.
The system 26, using information from the sensors 24, and information relating to the characteristics of the drainage solution 34 (derived using suitable monitoring methods and sensors), monitors the moisture content in the ore and controls the addition of water to the solution and hence to the irrigation network 14. The rate at which the solution is applied to the heap may be varied. Alternatively the solution may be applied to the heap in a “batch” mode i.e. application of the solution to the heap during one period is followed by a period in which no solution is applied to the heap, and so on.
The chloride ions (block 28) are introduced into the solution 16 using at least one of the following:
The sulphuric acid (block 30) may be added directly to the ore during a process of agglomeration or may be added to the solution 16 which in turn is applied to the ore 12 during an agglomeration phase or via the irrigation network 14.
In order to achieve the desired copper to iron ratio, which should prevail during the pre-treatment phase, various techniques may be employed. These include one or more of the following:
During the pre-treatment phase, with the establishment of a solution potential exceeding 700 mV SHE, oxidation of secondary covellite (a product of first step chalcocite oxidation), and of native covellite, by ferric iron, is enhanced:
During the active leach cycle the ore in the heap is irrigated with a leach solution 60. Copper leached from the heap is recovered from the draining solution 34 via a solvent extraction process 64. The leach solution 60 has a pH less than pH 2.5, achieved, as appropriate, by the addition of sulphuric acid 30. Optionally, the leach solution includes hydrochloric acid 66. The leach solution may also contain copper, iron and other anion and cation species 70 originating from processed water employed in the leaching cycle or dissolved from the ore which is being treated.
During the solvent extraction process 64 use may be made of one or more copper-loaded, organic washing stages 72 to promote an electrolyte chloride ion concentration below 50 ppm. The recovered copper is designated 74.
Tests were conducted in batch reactors at 25° C. containing various concentrations of copper (as shown in
Solutions potentials were measured over time in hours in batch reactors with natural air diffusion into an ore bed i.e. there was no forced aeration. This was at 25° C. The reactors contained various concentrations of copper, indicated in
Number | Date | Country | Kind |
---|---|---|---|
12/6310 | Aug 2012 | ZA | national |
Filing Document | Filing Date | Country | Kind |
---|---|---|---|
PCT/IB2013/001810 | 8/21/2013 | WO | 00 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2014/030048 | 2/27/2014 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
20040144209 | Faine | Jul 2004 | A1 |
20050169823 | Faine | Aug 2005 | A1 |
20070014709 | Moyes | Jan 2007 | A1 |
20110150729 | Liu | Jun 2011 | A1 |
20120308450 | Pereira | Dec 2012 | A1 |
Number | Date | Country |
---|---|---|
WO 2012001501 | Jan 2012 | WO |
Entry |
---|
PCT/IB2013/001810 International Search Report dated Jan. 7, 2014 (2 pages). |
PCT/IB2013/001810 Written Opinion of the International Preliminary Examining Authority dated Aug. 18, 2014 (4 pages). |
PCT/IB2013/001810 International Preliminary Report on Patentability dated Nov. 7, 2014 (4 pages). |
Article, Herreros et al.; “Leaching of sulfide copper ore in a NaCl—H2SO4—O2 media with acid pre-treatment”, Hydrometallurgy, Elsevier Scientific Publishing Cy, Amsterdam, NL, vol. 89, No. 3-4 Oct. 25, 2007 pp. 260-268, XP022314570; ISSN: 0304-386X, DOI: the whole document. |
Number | Date | Country | |
---|---|---|---|
20150232963 A1 | Aug 2015 | US |